Amine functional adducts and curable compositions comprising same

ABSTRACT

A multi-component curable composition which is reactive upon admixing of the components and wherein the composition comprises:
         A. a first component which comprises:
           (i) a first amine functional adduct which comprises the reaction product of a stoichiometric excess of a diamine and a compound having an epoxide group and an alpha, beta unsaturated carbonyl group;   
           B. a second component which comprises:
           (i) at least one compound having an average of more than 2.0 groups per molecule which are reactive with amines.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. non-provisional patentapplication Ser. No. 12/198,957 filed on Aug. 27, 2008, now U.S. Pat.No. 8,101,690 issued on Jan. 24, 2012, and which in turn claims thebenefit of U.S. provisional patent application No. 60/969,250 filed onAug. 31, 2007, the entirety of which is hereby incorporated byreference.

This invention relates to an amine functional adduct which comprises thereaction product of a (i) stoichiometric excess of a diamine and (ii) acompound having both an epoxide group and an alpha, beta unsaturatedcarbonyl group. This invention also relates to curable compositionsincorporating that adduct. The amine functional adduct will have anaverage of at least 2.0 primary or secondary amine groups per molecule,and it can be utilized in a variety of applications such as a chainextender or as a crosslinker with materials reactive with amines such asalpha, beta unsaturated carbonyl compounds, polyepoxides,polyisocyanates, etc.

1. Amine Functional Adduct of a Stoichiometric Excess of a Diamine and aCompound Having an Alpha, Beta Unsaturated Carbonyl Group

One aspect of this invention involves the reaction product obtained bythe reaction of a stoichiometric excess of a diamine and a compoundhaving both an epoxy group and an alpha, beta unsaturated carbonylgroup. In this preparation, the amine groups of the starting diaminewill react with the alpha, beta unsaturated carbonyl group via a Michaelreaction and also will react by addition with the epoxy group to producethe new amine functional adduct. As used herein with respect to thisadduct, the term “stoichiometric excess” means that at least 2.0 aminehydrogens from the starting diamine are present for each equivalent ofepoxy and each equivalent of alpha, beta unsaturated carbonyl groupcombined. For many applications it is useful to utilize more than 2.0equivalents of amine for each of the combined total number ofequivalents of epoxy and alpha, beta unsaturated carbonyl.

For those applications where it is desirable to minimize the molecularweight and viscosity of the final product it is convenient to use arelatively large stoichiometric excess of the diamine starting materialand it is convenient to add the compound having the epoxy group and thealpha, beta unsaturation to the diamine. For many such applications itis convenient to use an amount of diamine to provide a ratio of at least4:1, and for certain applications at least about 5:1, and for certainapplications at least about 6:1 and for other applications about 10:1 orhigher, of amine equivalents to combined equivalents of epoxy and alpha,beta unsaturated carbonyl groups. For many embodiments of thisinvention, admixing the components to provide ratios of between about2:1 to 20:1 of amine equivalents to combined equivalents of epoxy andalpha, beta unsaturated carbonyl groups can be a useful process forpreparing the adduct.

The reaction of the diamine and the compound having both an epoxy groupand an alpha, beta unsaturated carbonyl group is exothermic and canconveniently be conducted at temperatures ranging from room temperatureup to about 170° C. or higher. In one useful process for preparing theadduct, the starting diamine can be heated to about 50-60° C. and thecompound having an alpha, beta unsaturated carbonyl group and an epoxygroup can be added to the heated amine and maintained at a suitablereaction temperature until the reaction has proceeded to the desiredextent. The epoxy/alpha, beta unsaturated carbonyl compound can be addedall at once, or in a gradual or dropwise fashion if desired. If desired,the reaction mixture could also include a polymerization inhibitor suchas hydroquinone.

The amine-functional adduct reaction product present in the finalreaction mixture could be separated from the excess unreacted diaminestarting material by conventional separation techniques such asdistillation of the remaining unreacted diamine, but in many cases, suchas those where the amine-functional adduct will be utilized as acrosslinker or chain extender, it is often practical and cost effectiveto use the entire final reaction mixture which comprises theamine-functional adduct and the unreacted excess diamine startingmaterial as is without further purification since the unreacted diaminestarting material has the same general type of chemical functional groupas the adduct product itself, and will also function as a crosslinker,chain extender, or similar reactant in any subsequent reaction. In thesesituations it is often practical to use very large excesses of thediamine starting material.

Compounds having both an alpha, beta unsaturated carbonyl group, such as(meth)acrylic functionality, and an epoxy group are well known in theart. As used herein, the term “(meth)acryl” is meant to include bothacrylic and methacrylic structures. Compounds having both an epoxy groupand an alpha, beta unsaturated carbonyl group are readily prepared bythe esterification of carboxylated monomers, such as acrylic ormethacrylic acid, with glycidol or with epichlorohydrin followed bydehydrohalogenation. Representative compounds include the glycidyl(meth)acrylates, such as glycidyl acrylate and glycidyl methacrylate.Mixtures of more than one of the unsaturated glycidyl compounds can alsobe utilized.

The diamines which are useful in the production of this adduct can beany diamine having primary and/or secondary amine groups. For someapplications, primary diamines are especially useful. Representativediamines include aliphatic diamines such as ethylene diamine,1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane,2-methyl-1,5-diaminopentane, 1,6-diaminohexane, bis(6-aminohexyl)ether,cycloaliphatic diamines such as isophorone diamine,4,4′-methylene-bis-cyclohexylamine,bis(3-methyl-4-aminocyclohexyl)methane (BMACM),2,2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP),2,6-bis(aminomethyl)norbornane (BAMN), and cyclohexane diamine,heterocyclic diamines such as 3,4 diaminofuran and piperazine, andaromatic diamines such as m- or p-phenylenediamine, 2,4- or2,6-diaminotoluene, and 4,4′diaminodiphenylmethane. In some embodimentsit is useful to utilize only non-aromatic amines. In some embodiments,cycloaliphatic diamines are particularly useful. Mixtures of more thanone diamine can also be utilized.

For some embodiments it is preferred that the amine-functional adductitself would have a number average molecular weight less than about1500, or less than 1000, or less than 900, or less than 800, or lessthan 700, or less than 500 to provide products having relatively lowviscosities.

2. Curable Compositions Comprising the Amine-Functional Adduct

In a further embodiment of this invention, the amine-functional adductprepared as the reaction product of a stoichiometric excess of a diamineand a compound having an epoxide group and an alpha, beta unsaturatedcarbonyl group can be utilized in multi-component curable compositionswherein the components are reactive upon admixing the components, andwherein the first component comprises this adduct, optionally incombination with one or more other polyamines, including other polyamineadducts, and the second component comprises at least one compound havingan average of more than 2.0 groups per molecule which are reactive withamines. These reactive groups representatively would include, forexample, epoxy, alpha, beta unsaturated carbonyl groups and isocyanategroups. In some embodiments it is useful to utilize compounds havingepoxy groups and/or compounds having alpha, beta unsaturated carbonylgroups in the curable compositions.

In an additional embodiment, this invention relates to a multi-componentcurable composition which is reactive upon admixing of the componentsand wherein the composition comprises:

-   -   A. a first component which comprises:        -   (i) an amine-functional adduct which comprises the reaction            product of a stoichiometric excess of a diamine and a            compound having both an epoxide group and an alpha, beta            unsaturated carbonyl group;        -   (ii) optionally, at least one additional polyamine having an            average of at least 2.0 primary or secondary amine groups            per molecule; and    -   B. a second component which comprises at least one compound        having an average of more than 2.0 groups per molecule which are        reactive with amines.

In another embodiment, this invention relates to a multi-componentcurable composition which is reactive upon admixing of the componentsand wherein the composition comprises:

-   -   A. a first component which comprises:        -   (i) a first amine functional adduct which comprises the            reaction product of a stoichiometric excess of a first            diamine and a compound having an epoxide group and an alpha,            beta unsaturated carbonyl group; and        -   (ii) a second amine functional adduct which comprises the            reaction product of a stoichiometric excess of a second            diamine and a polyepoxide having an average of at least 2.0            epoxy groups per molecule; and        -   (iii) optionally, an additional polyamine having an average            of at least 2.0 primary or secondary amine groups per            molecule; and    -   B. a second component which comprises:        -   (i) at least one polyepoxide having an average of at least            2.0 epoxy groups per molecule; and        -   (ii) at least one poly (meth)acrylate having an average of            at least 2.0 (meth)acrylate groups per molecule;            and wherein the first diamine and the second diamine may be            the same or different.

2. (a) Amine Functional Adduct of a Stoichiometric Excess of a Diamineand a Polyepoxide

In some embodiments of the curable compositions of this invention it isuseful to incorporate a second amine-functional adduct to be used incombination with the first amine-functional adduct described inSection 1. One useful second amine-functional adduct comprises thereaction product of a stoichiometric excess of a diamine and apolyepoxide having an average of at least 2.0 epoxy groups per molecule.As used herein, with respect to this adduct, the term “stoichiometricexcess” means that at least 2.0 amine hydrogens from the startingdiamine are present for each equivalent of epoxy in the polyepoxide. Formany applications it is useful to utilize more than 2.0 equivalents ofamine for each equivalent of epoxy to prepare the adduct. For manyapplications, such as those where it is desirable to minimize themolecular weight and viscosity of the final product, it is convenient touse a relatively large stoichiometric excess of the diamine startingmaterial. In some embodiments of this invention, it can be useful toincorporate at least about 5.0 and sometimes at least about 10.0, andsometimes at least about 15.0, and sometimes at least about 20.0, andsometimes at least about 25.0, and sometimes at least about 30.0equivalents of amine for each equivalent of epoxy in the preparation ofthis second amine functional adduct. The very high excess of aminefunctionality can help to minimize the molecular weight and viscosity ofthe final product.

In one useful process for preparing the adduct, the starting diamine canbe heated to about 50-60° C. and the polyepoxide can be added to theheated amine and maintained at a suitable reaction temperature until thereaction has proceeded to the desired extent. The polyepoxide can beadded all at once, or in a gradual or dropwise fashion if desired. Ifdesired, the reaction mixture could also include a polymerizationinhibitor such as hydroquinone.

The reaction of the diamine and the polyepoxide is exothermic and canconveniently be conducted at temperatures ranging up to about 170° C. orhigher. The amine-functional adduct reaction product could be separatedfrom the excess unreacted diamine starting material by conventionalseparation techniques such as distillation, but in many cases, such asthose where the amine-functional adduct will be utilized as acrosslinker or chain extender, it is often practical and cost effectiveto use the entire reaction mixture which comprises the amine-functionaladduct and the unreacted excess diamine starting material as is withoutfurther purification since the unreacted diamine starting material hasthe same general type of chemical functional group as the adduct productitself, and will also function as a crosslinker, chain extender, orsimilar reactant in any subsequent reaction.

The diamine which is useful in the preparation of this secondamine-functional adduct can be any diamine having primary and/orsecondary amine groups. The representative diamines taught for the firstamine-functional adduct of Section 1 hereof, are also representative ofdiamines that might be utilized in the production of this second adduct.For some applications, cycloaliphatic diamines are useful. Thepolyepoxides which are useful in the preparation of this second adductshould have an average of at least 2.0 epoxy groups per molecule. Forsome embodiments it is useful to select a polyepoxide having an averageof between about 2.0 and about 4.0 epoxy groups per molecule.

Representative polyepoxides useful in the preparation of the secondadduct can be any polyepoxide having an average of at least 2.0 epoxygroups per molecule and include the glycidyl ethers of aliphatic oraromatic diols or polyols such as the polyepoxy functional novolac,bisphenol and aliphatic and cycloaliphatic epoxies. Some specificexamples of useful polyepoxides include butanediol diglycidyl ether,neopentylglycol diglycidyl ether, diglycidyl1,2-cyclohexanedicarboxylate, poly(propylene glycol) diglycidyl ether,resorcinol diglycidyl ether, triglycidyl ethers of glycerin, triglycidylisocyanurate, trimethylolpropane triglycidyl ether, novolac epoxyresins, bisphenol A epoxy resins, etc. Polyglycidyl ethers are wellknown in the art and can be conveniently prepared by the reaction of anepihalohydrin, such as epichlorohydrin, with a compound having at leasttwo hydroxyl groups, such as an aliphatic or cycloaliphatic polyol or apolyhydric phenol. Other polyepoxides include the glycidyl esters, suchas those typically obtained by the reaction of polycarboxylic acids withepihalohydrins and alkali metal hydroxides. Epoxy novolac resins areuseful in some embodiments of this invention, and are representativelyprepared by reacting an epihalohydrin with the condensation product ofan aldehyde with a polyhydric phenol.

Polyepoxides can also be prepared by the polymerization of unsaturatedepoxy functional monomers such as glycidyl acrylate with otherunsaturated monomers. For some embodiments of this invention, aliphaticpolyepoxides and/or epoxy novolacs are useful.

2. (b) Optional Additional Polyamines

For some embodiments of the curable compositions of this invention itmay be useful to also incorporate additional polyamines having primaryand/or secondary amine groups. Frequently it is practical to incorporateadditional polyamines into the first component of the curablecomposition by utilizing the unpurified reaction mixture from theproduction of the first amine adduct and the second amine adduct, sincethe remaining unreacted diamine starting material will be capable ofreacting as a polyamine. Other diamines, such as those taught for use inthe production of the adducts themselves, can be incorporated. For someembodiments of the curable compositions it is useful to incorporate atleast some polyamines having an average of more than 2.0 primary orsecondary amine groups per molecule to provide greater branching orcrosslinking to the system.

Representative polyamines having an average of more than 2.0 aminegroups per molecule include diethylenetriamine,N,N′-dimethyldiethyltriamine, cyclohexyl-1,2,4-triamine,triethylenetetramine, cyclohexyl-1,2,4,5-tetramine,tetramethylenepentamine, etc. Polyamines can also be prepared by methodswell known in the art such as by the polymerization of acrylic or otherunsaturated monomers having primary or secondary amine functionality, orby the reaction of amines having at least two primary amine groups permolecule with a polycarboxylic acid to form polyamide amines. Otherpolyamines such as the Jeffamine® polyoxypropyleneamines available fromHuntsman Chemicals, Inc. are also practical. Mixtures of two or moreadditional polyamines can also be utilized. For some embodiments of thisinvention, aliphatic and cycloaliphatic amines are useful due to some oftheir properties such as clarity and resistance to yellowing.

The first amine adduct and optionally the second amine adduct andoptionally the additional polyamines will typically comprise onecomponent of a multicomponent curable composition. The second componentof the multicomponent composition will comprise at least one compoundhaving an average of more than 2.0 groups per molecule which arereactive with amines, such as polyepoxides, poly(meth)acrylates orpolyisocyanates, or mixtures thereof.

2. (c) Polyepoxide Compounds

Polyepoxide compounds which are useful in the curable compositions ofthis invention can include any polyepoxide having an average of at least2.0 epoxy groups per molecule. Polyepoxides are well known in the artand the polyepoxides listed in Section 2(a) above are alsorepresentative examples of some of the polyepoxides that can be utilizedin the curable compositions of this invention. Mixtures of more than onepolyepoxide are also practical.

2. (d) Poly(meth)acrylate Compounds

It is also useful in some embodiments of the curable compositions ofthis invention to incorporate compounds having an average of at least2.0 (meth)acrylate or other alpha, beta unsaturated carbonyl groupswhich are capable of Michael-type reactions with amines.Poly(meth)acrylate compounds are well known in the art and can beconveniently prepared by a variety of methods. Suitable unsaturatedesters can be prepared by reacting acrylic acid or methacrylic acid withpolyhydric alcohols such as ethylene glycol, 1,2- and 1,3- propyleneglycol, 1,4-butanediol, neopentyl glycol, 2-methyl-1,5-pentanediol,dimethylolcyclohexane, glycerol, trimethylolpropane, pentaerythritol,dipentaerythritol, etc. Also, the polyhydric alcohols could be convertedinto ether alcohols of higher molecular weights by alkoxylation with amonoepoxide such as propylene oxide or ethylene oxide prior to reactionwith the unsaturated acids. Representative useful compounds having anaverage of at least 2.0 alpha, beta unsaturated carbonyl groups includepolyethylene glycol di(meth)acrylate, 1,3-butylene glycoldi(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylatedbisphenol A di(meth)acrylate, trimethylol propane tri(meth)acrylate,tris (2-hydroxyethyl)isocyanurate trimethacrylate, pentaerythritoltri(meth)acrylate, and dipentaerytritol penta(meth)acrylate. Mixtures ofcompounds having at least 2.0 alpha, beta unsaturated groups are alsopractical. For some embodiments it is useful to utilize both adifunctional compound and also a compound having more than two alpha,beta unsaturated carbonyl groups. For some embodiments of the curablecompositions, acrylates are preferred over methacrylates due to theirrelatively faster reaction rates.

2. (e) Polyisocyanate Compounds

Polyisocyanates can also be useful in reacting with the amine functionaladducts. Polyiscocyanates useful in the compositions of this inventionhave an average of at least two isocyanate groups per molecule.Representative polyisocyanates having two or more isocyanate groups permolecule include the aliphatic compounds such as ethylene, trimethylene,tetramethylene, pentamethylene, hexamethylene, 1,2-propylene,1,2-butylene, 2,3-butylene, 1,3-butylene, ethylidene and butylidenediisocyanates; the cycloalkylene compounds such as3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, and the1,3-cyclopentane, 1,3-cyclohexane, and 1,2-cyclohexane diisocyanates;the aromatic compounds such as m-phenylene, p-phenylene, 4,4′-diphenyl,1,5-naphthalene and 1,4-naphthalene diisocyanates; thealiphatic-aromatic compounds such as 4,4′-diphenylene methane, 2,4- or2,6-toluene, or mixtures thereof, 4,4′-toluidine, and 1,4-xylylenediisocyanates; the nuclear substituted aromatic compounds such asdianisidine diisocyanate, 4,4′-diphenylether diisocyanate andchlorodiphenylene diisocyanate; the triisocyanates such as triphenylmethane-4,4′,4″-triisocyanate, 1,3,5-triisocyanate benzene and2,4,6-triisocyanate toluene; and the tetraisocyanates such as4,4′-diphenyl-dimethyl methane-2 ,2′-5,5′-tetraisocyanate; thepolymerized polyisocyanates such as tolylene diisocyanate dimers andtrimers, and other various polyisocyanates containing biuret, urethane,and/or allophanate linkages.

In those embodiments where the first component comprises the first amineadduct and any additional amines and/or amine adducts, and the secondcomponent comprises a polyisocyanate, the ratio of equivalents ofisocyanate to active hydrogen in the first component can be widelyvaried within the practice of this invention. In such a formulation thepolyisocyanate will typically be present at a level to provide at leastabout 0.3, and for some applications about 0.5 to about 2.0, and forsome applications about 0.7 to about 1.3 equivalents of isocyanate foreach equivalent of active hydrogen.

In one embodiment, the multi-component curable compositions willcomprise a first component, comprising the first amine adduct and anyadditional amines and/or amine adducts, and a second component,comprising the materials reactive with amines such as the polyepoxide,and/or the alpha, beta unsaturated carbonyl compounds. These curablecompositions would typically be admixed in amounts to provide anequivalents ratio of amine equivalents to equivalents of groups reactivewith amines of at least about 0.3 and for some applications at leastabout 0.5, and for some applications at least about 0.9 and in somecases at least about 1.0 and in some embodiments at least about 1.5, andin some cases at least about 2.0 for each equivalent of groups reactivewith amines. The relative weight ratios of the first amine adduct andthe optional second amine adduct and the optional additional polyaminescan vary widely within the practice of this invention. For someembodiments the relative weight ratios would be from 0.1 to 100% of thefirst amine functional adduct, from 0.0 to 99.9% of the optional secondamine functional adduct, and from 0.0 to 99.9% of any additionalpolyamines. In one embodiment of the curable compositions of thisinvention, useful weight ratios would be from 1.0 to 97% of the firstamine functional adduct, 1.0 to 97% of the second amine functionaladduct and 1.0 to 97% of any additional polyamines. In anotherembodiment, useful relative weight ratios would be 3.0 to 35% of thefirst amine functional adduct, 3.0 to 35% of the second amine functionaladduct, and 30 to 94% of the additional polyamines.

Similarly, the relative weight ratios of the polyepoxides and thepoly(meth)acrylate compounds which are used in some of the curablecompositions can vary widely if both are used. For some embodiments, therelative weight ratios would be from 0.1% to 99.9% of the polyepoxidesand from 0.1 to 99.9% of the poly(meth)acrylate compounds. In anotherembodiment of the curable compositions, the relative weight ratios wouldbe from 5.0% to 65.0% poly(meth)acrylate and 35% to 95% polyepoxide. Inanother embodiment the relative weight ratios would be from 10% to 40%of the poly(meth)acrylate and 60% to 90% polyepoxide.

The curable compositions of this invention are reactive upon mixing andcan typically be cured at temperatures ranging from about roomtemperature up to about 175° C. or higher. For many applications it isuseful to allow the composition to cure at room temperature.

When the curable compositions are utilized as coatings, the coatings canbe clear coatings or they may contain pigments or dyes as is well knownin the art. Representative opacifying pigments include white pigmentssuch as titanium dioxide, zinc oxide, antimony oxide, etc. and organicor inorganic chromatic pigments such as iron oxide, carbon black,phthalocyanine blue, etc. The coatings may also contain extenderpigments such as calcium carbonate, clay, silica, barites, talc, etc.

The coatings may also contain other additives such as flow agents,catalysts, diluents, solvents, ultraviolet light absorbers andstabilizers, flexibilizers, and adhesion promoters.

Since the curable compositions of this invention are typically providedas multi-package systems which must be mixed together prior to use, thepigments, catalysts and other additives can be conveniently added to anyor all of the appropriate individual packages. The curable compositionsof the invention may typically be applied to any substrate such asconcrete, asphalt, metal, plastic, wood, glass, synthetic fibers, etc.by brushing, dipping, roll coating, squeegee, flow coating, spraying,in-mold coating, or other method conventionally employed in the coatingindustry.

In one embodiment of this invention, the curable composition of thisinvention can be utilized as a curable flooring material. In thisapplication, the curable composition can be applied as a very highsolids material and will cure very quickly, sometimes allowing amulti-coat application which will cure sufficiently to walk on withintwelve hours or less at room temperature. In such an application, it istypical to apply an initial coat to a concrete or other floor substrate.For many applications the curable coating is poured onto the floor andspread with a squeegee or other applicator to achieve a wet filmthickness of between about 15 to 35, and typically 20 to about 30, mils.This application can then be followed by the optional broadcast of soliddecorative and/or protective materials such as colored pigments,metallic flakes, glass beads, fluorescent particles, garnet, slipresistant particles or other materials onto the wet surface of thecoating before it is completely cured. This initial layer is allowed tocure or dry for several hours and the process can be repeated with oneor more additional coating layers applied thereto, optionally followedby another broadcast of coloring material. Finally, a clear coat may beapplied to that surface and allowed to dry. Due to the extremely fastcure of the curable coatings of this invention it is possible tocomplete such a multicoat application and walk on the cured coating inless than 24 hours, and frequently in less than about 12 hours.

The following examples have been selected to illustrate specificembodiments and practices of advantage to a more complete understandingof the invention. Unless otherwise stated, “parts” means parts-by-weightand “percent” is percent-by-weight, equivalent weight is on a weightsolids basis, and molecular weight is number average molecular weight asdetermined relative to polystyrene standards. As used herein, the term“reaction mixture” includes both the reaction product adduct and theunreacted starting materials such as any unreacted stoichiometric excessof diamine starting material.

EXAMPLE 1 Preparation of an Amine Functional Adduct Comprising theReaction Product of a Stoichiometric Excess of a Diamine and a MonomerHaving an Alpha, Beta Unsaturated Carbonyl Group and an Epoxide Group

A reaction vessel equipped with an agitator, addition funnel andcondenser was charged with 1000 parts (approximately 19.05 equivalents)of PACM (4,4′-methylene-bis-cyclohexylamine) which had been preheated to50° C. The temperature was increased to 62° C. and 200 parts(approximately 2.82 equivalents) of GMA (glycidyl methacrylate) wasadded to the reaction vessel and agitated. The agitation was continuedand the external heat was turned off. The mixture was allowed toexotherm to about 115 to 120° C. The mixture was maintained underagitation for about 50 minutes and then the temperature was increased toabout 145° C. and maintained at that temperature for about 30 minutes.The reaction mixture comprising the amine functional adduct reactionproduct and the unreacted starting material was then allowed to cool.

EXAMPLE 2 Preparation of an Amine Functional Adduct Comprising theReaction Product of a Stoichiometric Excess of a Diamine and aPolyepoxide

A reaction vessel equipped with an agitator, additional funnel andcondenser was charged with 1000 parts (approximately 23.5 equivalents)of IPDA (isophorone diamine) which had been preheated to 60° C. 200parts (approximately 1.2 equivalents) of CVC 8240 (Novolac epoxy resinfrom CVC Specialty Chemicals Inc. having an epoxide equivalent weight ofapproximately 170) was added to the reaction vessel and agitated. Themixture was allowed to exotherm to about 108 to 112° C. The mixture wasmaintained under agitation for about 40 minutes and then the temperaturewas increased to about 150° C. and maintained at that temperature forabout 30 minutes. The reaction mixture comprising the amine functionaladduct reaction product and the unreacted starting material was thenallowed to cool.

EXAMPLE 3 Preparation of Blends of Amine Functional Materials as a FirstComponent

The reaction mixtures of Examples 1 and 2 (1,200 parts of each) wereblended together. Triethylenetetramine (TETA, 243.77 parts) was added tothis mixture under agitation and allowed to slowly blend in for 5minutes. Benzyl alcohol (32.11 parts) was then added and mixed. Thistotal mixture equates to 44.85% by weight of each of the reactionmixtures of Examples 1 and 2, 9.11% TETA, and 1.20% benzyl alcohol.

EXAMPLE 4 Preparation of Second Component

A blend was prepared by admixing neopentyl glycol diglycidyl ether(42.94 parts), trimethylolpropane triglycidyl ether (32.24 parts),trimethylolpropane triacrylate (22.43 parts), polymethyl siloxanedefoamer (0.16 parts), polyether modified poly-dimethyl-siloxane flowagent (1.13 parts), andbis(1,2,2,6,6-pentamethyl-4-piperidinyl)-sebacate light stabilizer (1.09parts).

EXAMPLE 5 Preparation of a Curable Composition

A curable composition was prepared by admixing one volume portion of thefirst component prepared as described in Example 3 (amine portion) andtwo volume portions of the second component prepared as described inExample 4 (epoxy and poly(meth)acrylate portion). This provides anequivalent ratio of approximately 1.03 amine equivalents for eachequivalent of alpha, beta unsaturated carbonyl and epoxy. When appliedto a substrate and allowed to cure the curable composition reactsquickly to form a hard, resistant cured film.

While this invention has been described by a specific number ofembodiments, other variations and modifications may be made withoutdeparting from the spirit and scope of the invention as set forth in theappended claims.

The entire disclosure of all applications, patents and publicationscited herein are hereby incorporated by reference.

1. A multi-component curable composition which is reactive upon admixingof the components and wherein the composition comprises: A. a firstcomponent which comprises: (i) a first amine functional adduct whichcomprises the reaction product of a stoichiometric excess of a diamineand a compound having an epoxide group and an alpha, beta unsaturatedcarbonyl group; B. a second component which comprises: (i) at least onecompound having an average of more than 2.0 groups per molecule whichare reactive with amines.
 2. The composition of claim 1 wherein thefirst amine functional adduct comprises the reaction product of astoichiometric excess of a diamine and glycidyl (meth)acrylate.
 3. Thecomposition of claim 1 wherein the diamine comprises a cycloaliphaticdiamine.
 4. The composition of claim 1 wherein the diamine comprises4,4′-methylene-bis-cyclohexylamine.
 5. The composition of claim 1wherein the first amine functional adduct has a number average molecularweight less than about 1,500.
 6. The composition of claim 1 wherein thefirst amine functional adduct is the reaction product obtained byadmixing the diamine and the compound having an epoxide group and analpha beta unsaturated carbonyl at amounts to provide at least 4.0equivalents of amine for each equivalent of epoxy and of alpha, betaunsaturated carbonyl combined.
 7. The composition of claim 1 wherein thefirst component also comprises at least one additional polyamine havingan average of at least 2.0 primary or secondary amine groups permolecule.
 8. The composition of claim 1 wherein the at least onecompound having an average of more than 2.0 groups per molecule whichare reactive with amines comprises a polyepoxide.
 9. The composition ofclaim 1 wherein the at least one compound having an average of more than2.0 groups per molecule which are reactive with amines comprises atleast one poly (meth)acrylate having an average of more than 2.0 (meth)acrylate groups per molecule.
 10. The composition of claim 9 wherein theat least one poly (meth)acrylate comprises a tri (meth)acrylate.
 11. Thecomposition of claim 1 wherein the first component and the secondcomponent are present in an amount to provide a ratio of amineequivalents to equivalents of compounds reactive with amines of at least0.9:1.
 12. The composition of claim 1 wherein the first component andthe second component are present in an amount to provide a ratio ofamine equivalents to equivalents of compounds reactive with amines of atleast 1:1
 13. The composition of claim 1 wherein the first component andthe second component are present in an amount to provide a ratio ofamine equivalents to equivalents of compounds reactive with amines ofbetween 1:1 to about 1.5:1.